Ink jet ink composition

ABSTRACT

An ink jet ink composition of water, a humectant, and a hyperbranched polymeric dye of a hyperbranched polymer having a dye chromophore pendant on the polymer chain or incorporated into the polymer backbone.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] Reference is made to commonly assigned, co-pending U.S. patentapplication Ser. Nos.:

[0002] ______ by Chen et al., filed of even date herewith (Docket82818), entitled “Ink Jet Printing Method”;

[0003] ______ by Wang, filed of even date herewith (Docket 83086),entitled “Process for Manufacture of Soluble, Highly BranchedPolyamides, And At Least Partially Aliphatic Highly Branched PolyamidesObtained Therefrom”;

[0004] ______ by Wang et al., filed of even date herewith (Docket82298), entitled “Water Soluble and Dispersible Highly BranchedPolyamides”;

[0005] ______ by Wang, filed of even date herewith (Docket 82401),entitled “Highly Branched Polyesters Through One-Step PolymerizationProcess”; and

[0006] Ser. No. 09/697,205 by Wang, filed Oct. 26, 2000, entitled“Highly Branched Polyesters Through One-Step Polymerization Process”.

FIELD OF THE INVENTION

[0007] This invention relates to an ink jet ink composition comprising ahyperbranched polymeric dye comprising a hyperbranched polymer having adye chromophore pendant on the polymer chain or incorporated into thepolymer backbone.

BACKGROUND OF THE INVENTION

[0008] Ink jet printing is a non-impact method for producing images bythe deposition of ink droplets in a pixel-by-pixel manner to animage-recording element in response to digital signals. There arevarious methods which may be utilized to control the deposition of inkdroplets on the image-recording element to yield the desired image. Inone process, known as continuous ink jet, a continuous stream ofdroplets is charged and deflected in an imagewise manner onto thesurface of the image-recording element, while unimaged droplets arecaught and returned to an ink sump. In another process, known asdrop-on-demand ink jet, individual ink droplets are projected as neededonto the image-recording element to form the desired image. Commonmethods of controlling the projection of ink droplets in drop-on-demandprinting include piezoelectric transducers and thermal bubble formation.Ink jet printers have found broad applications across markets rangingfrom industrial labeling to short run printing to desktop document andpictorial imaging.

[0009] The inks used in the various ink jet printers can be classifiedas either dye-based or pigment-based. A dye is a colorant which isdissolved in the carrier medium. A pigment is a colorant that isinsoluble in the carrier medium, but is dispersed or suspended in theform of small particles, often stabilized against flocculation andsettling by the use of dispersing agents. The carrier medium can be aliquid or a solid at room temperature in both cases. Commonly usedcarrier media include water, mixtures of water and organic co-solventsand high boiling organic solvents, such as hydrocarbons, esters,ketones, etc.

[0010] In traditional dye-based inks, no particles are observable underthe microscope. Although there have been many recent advances in the artof dye-based ink jet inks, such inks still suffer from deficiencies suchas low optical densities on plain paper and poor light-fastness. Whenwater is used as the carrier, such inks also generally suffer from poorwater fastness and poor smear resistance. These problems can beminimized by replacing the dyes used in ink formulations with insolublepigments. In general, pigments are superior to dyes with respect towaterfastness, lightfastness, and stability towards pollutants in theair. However, the pigment inks tend to be unstable and settle out fromthe liquid vehicle over a long storage time. Pigment inks also have atendency to clog the orifices of the printhead resulting indeterioration of print quality.

[0011] Accordingly, there is a need for inks having advantages of bothdye-based inks and pigment based inks that have good lightfastness,stability towards pollutants, waterfastness and reliability in theprinthead.

[0012] Polymeric colorants, such as polymeric dyes are known. Incomparison with ordinary colorants, polymeric colorants offer theadvantage of allowing a range of physical properties. Their solubility,absorption, migration, and viscosity are tunable and they do notsublime, are non-abrasive, and generally have low toxicity.

[0013] U.S. Pat. No. 4,644,708 discloses-an ink composition comprisingwater and a polymeric dye comprised of the reaction product of awater-soluble polymer with a reactive dye. However, there is a problemwith this dye in that its viscosity is high, resulting in poorfirability from a thermal ink jet printhead.

[0014] U.S. Pat. No. 5,098,475 discloses the preparation of dendrimericdyes by reacting a dendrimer with a dye and using the dendrimeric dye inink formulations. However, there is a problem with these dendrimericdyes in that dendrimers are typically prepared through lengthymulti-step syntheses, and their availability is limited to a small groupof functional monomers.

[0015] It is an object of this invention to provide an ink jet inkcomposition that, when printed, provides an image which has improvedwaterfastness, lightfastness, and stability towards pollutants such asozone. It is another object of the present invention to provide an inkjet ink composition that has improved firability through an ink jetprinthead.

SUMMARY OF THE INVENTION

[0016] These and other objects are achieved in accordance with thisinvention which relates to an ink jet ink composition comprising water,a humectant, and a hyperbranched polymeric dye comprising ahyperbranched polymer having a dye chromophore pendant on the polymerchain or incorporated into the polymer backbone.

[0017] It has been found that this ink jet ink composition, whenprinted, provides an image which has improved waterfastness,lightfastness, and stability towards pollutants such as ozone and hasimproved firability through an ink jet printhead.

DETAILED DESCRIPTION OF THE INVENTION

[0018] Any hyperbranched polymer may be used in the invention to whichis attached a pendant dye chromophore or which has a dye chromophoreincorporated into the polymer backbone. A hyperbranched polymer isdefined as a polymer formed by polymerization of one or more branchingmonomers as described in J. Am. Chem. Soc., 74, p2718 (1952), thedisclosure of which is hereby incorporated by reference. In general,hyperbranched polymers can be made through chain polymerization orcondensation polymerization processes, as described in U.S. Pat. No.4,857,630, the disclosure of which is hereby incorporated by reference.

[0019] Hyperbranched polymers which may be used in this inventioncontaining a dye either as a pendant group or in the backbone aredescribed in copending application Ser. No. ______ by Wang et al., filedof even date herewith (Docket 82298), entitled “Water Soluble andDispersible Highly Branched Polyamides” referred to above, and U.S. Pat.No. 6,252,025, the disclosures of which are hereby incorporated byreference.

[0020] In a preferred embodiment of the invention, the hyperbranchedpolymer having a dye chromophore pendant thereto which may be used hasthe formula:

HB-D_(n)

[0021] wherein:

[0022] HB is a hyperbranched polymer core;

[0023] D is a dye moiety; and

[0024] n is an integer of at least 2.

[0025] In another preferred embodiment, HB is a polyamide, polyester,polyether, vinylic polymer, polyimine, polysiloxane, polyesteramide orpolyurethane.

[0026] In still another preferred embodiment of the invention, HB isprepared by a chain polymerization of a monomer of the formula M¹-R¹-M²_(m) wherein (i) R¹ is a linear or branched alkyl, carbonyl, or aromaticmoiety; (ii), M¹ and M² are reactive groups that react independently ofeach other in which M¹ is a polymerization group and M² is a precursorof a moiety M²* which initiates the polymerization of M¹ as a result ofbeing activated; and (iii), m is an integer of at least 1.

[0027] In another preferred embodiment of the invention, HB is preparedby a condensation or addition polymerization of a monomer of the formulaM³-R²-M⁴ _(p) wherein (i) R² is a linear or branched alkyl or aromaticmoiety; (ii), M³ and M⁴ are groups that undergo a condensation oraddition reaction; and (iii), p is an integer of at least 2.

[0028] In another preferred embodiment of the invention, HB is preparedby a condensation or addition polymerization of a monomer of the formulaR²-M⁵ _(q) and R³-M⁶ _(t) wherein (i) R² is as defined above and R³ is alinear or branched alkyl or aromatic moiety; (ii), M⁵ and M⁶ are groupsthat undergo a condensation or addition reaction; and (iii), q is aninteger of at least 2 and t an integer of at least 3.

[0029] In another preferred embodiment of the invention, M¹ is anon-substituted or substituted vinylic group, M² is X, —CH₂X or—CH(CH₃)X wherein X is Cl, Br, I, S—C(═S), YR⁴R⁵ or —O—NR⁴R⁵, Y═O or N,and R⁴ and R⁵ are each independently —(CH₂)_(r) (r=1-12), —C₆H₅, —C(O)O,or C(O).

[0030] In another preferred embodiment of the invention, M³ and M⁴ areeach independently —COOH, —OH, —C(O)Cl, epoxy, anhydride, NH, or NH₂,and R² is —C₆H₃—, or —(CH₂)_(s)—C(R⁶)— wherein R⁶ is a linear orbranched alkyl or aromatic group and s is an integer of 1-12.

[0031] In another preferred embodiment of the invention, M⁵ and M⁶ areeach independently —COOH, —OH, —C(O)Cl, epoxy, anhydride, NH or NH₂, R³is —C₆H₄—, —C₆H₄—O—C₆H₄—, —C₆H₃, N(CH₂)₃—, —C₄H₈—, —C₆H₁₀—,

[0032] The dye chromophores which may be used in the present inventiongenerally include any of the reactive dyes capable of reacting with thehyperbranched polymer to become attached thereto. The bond between thehyperbranched polymer and dye can be a covalent bond or an ionic bond.These dyes typically comprise a chromophore, such as a mono- or poly-azodye, such as a pyrazoleazoindole dye as disclosed in U.S. patentapplication Ser. No. 09/689,184 filed Oct. 12, 2000; a basic dye, aphthalocyanine dye, a methine or polymethine dye, a merocyanine dye, anazamethine dye, a quinophthalone dye, a thiazine dye, an oxazine dye, ananthraquinone, or a metal-complex dye, such as those described in U.S.Pat. Nos. 5,997,622 and 6,001,161, i.e., a transition metal complex ofan 8-heterocyclylazo-5-hydroxyquinoline.

[0033] In still another preferred embodiment of the invention, thehyperbranched polymeric dyes (HBPD) have dye chromophores incorporatedinto the polymer backbone. These hyperbranched polymeric dyes can beprepared by any kind of polymerization process, similar to thosedescribed above for HB. At least one of the monomers used to prepareHBPD contains a dye chromophore.

[0034] In a preferred embodiment, the hyperbranched polymer having a dyechromophore incorporated into the polymer backbone is prepared by achain polymerization of a monomer of the formula M¹-R⁷-M² _(m) whereinR⁷ is a linear or branched alkyl, carbonyl, or aromatic moietycontaining a dye chromophore and M¹, M² and m are defined above.

[0035] In another preferred embodiment, the hyperbranched polymer havinga dye chromophore incorporated into the polymer backbone is prepared bya condensation or addition polymerization of a monomer of the formulaM³-R⁷-M⁴ _(p) wherein R⁷, M³, M⁴ and p are defined above.

[0036] In still another preferred embodiment, the hyperbranched polymerhaving a dye chromophore incorporated into the polymer backbone isprepared by a condensation or addition polymerization of a monomer ofthe formula R⁸-M⁵ _(q) and R⁹-M⁶ _(t) wherein R⁸ and R⁹ are eachindependently a linear or branched alkyl or aromatic moiety, at leastone of which contains a dye chromophore, and M⁵, M⁶, q and t are definedas above.

[0037] In yet still another preferred embodiment, the hyperbranchedpolymer having a dye chromophore incorporated into the backbone thereofis a polyamide, polyester, polyether, vinylic polymer, polyimine,polyesteramide or polyurethane.

[0038] In another preferred embodiment of the invention, the dyes usedto prepare the hyperbranched polymeric dyes generally include any of thereactive dyes with at least two reactive groups capable of reacting withitself (homopolymerization) or with other monomer(s) (copolymerization)to form the hyperbranched polymeric dyes in which dye chromophores areincorporated into the backbone.

[0039] Specific examples of hyperbranched polymeric dyes useful in theinvention include the following structures:

[0040] In general, the above hyperbranched polymeric dyes have amolecular weight from about 500 to about 50,000 and comprise from about0.2 to about 20%, preferably from about 0.5 to 8%, by weight of the inkjet composition.

[0041] A humectant is employed in the ink jet composition of theinvention to help prevent the ink from drying out or crusting in theorifices of the printhead. Examples of humectants which can be usedinclude polyhydric alcohols, such as ethylene glycol, diethylene glycol,triethylene glycol, propylene glycol, tetraethylene glycol, polyethyleneglycol, glycerol, 2-methyl-2,4-pentanediol 1,2,6-hexanetriol andthioglycol; lower alkyl mono- or di-ethers derived from alkyleneglycols, such as ethylene glycol mono-methyl or mono-ethyl ether,diethylene glycol mono-methyl or mono-ethyl ether, propylene glycolmono-methyl or mono-ethyl ether, triethylene glycol mono-methyl ormono-ethyl ether, diethylene glycol di-methyl or di-ethyl ether, anddiethylene glycol monobutylether; nitrogen-containing cyclic compounds,such as pyrrolidone, N-methyl-2-pyrrolidone, and1,3-dimethyl-2-imidazolidinone; and sulfur-containing compounds such asdimethyl sulfoxide and tetramethylene sulfone. A preferred humectant forthe composition of the invention is diethylene glycol, glycerol, ordiethylene glycol monobutylether.

[0042] Water-miscible organic solvents may also be added to the aqueousink of the invention to help the ink penetrate the receiving substrate,especially when the substrate is a highly sized paper. Examples of suchsolvents include alcohols, such as methyl alcohol, ethyl alcohol,n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol,t-butyl alcohol, iso-butyl alcohol, furfuryl alcohol, andtetrahydrofurfuryl alcohol; ketones or ketoalcohols such as acetone,methyl ethyl ketone and diacetone alcohol; ethers, such astetrahydrofuran and dioxane; and esters, such as, ethyl lactate,ethylene carbonate and propylene carbonate.

[0043] Surfactants may be added to adjust the surface tension of the inkto an appropriate level. The surfactants may be anionic, cationic,amphoteric or nonionic.

[0044] A biocide may be added to the composition of the invention tosuppress the growth of microorganisms such as molds, fungi, etc. inaqueous inks. A preferred biocide for the ink composition of the presentinvention is Proxel® GXL (Zeneca Specialties Co.) at a finalconcentration of 0.0001-0.5 wt. %.

[0045] The pH of the aqueous ink compositions of the invention may beadjusted by the addition of organic or inorganic acids or bases. Usefulinks may have a preferred pH of from about 2 to 10, depending upon thetype of dye being used. Typical inorganic acids include hydrochloric,phosphoric and sulfuric acids. Typical organic acids includemethanesulfonic, acetic and lactic acids. Typical inorganic basesinclude alkali metal hydroxides and carbonates. Typical organic basesinclude ammonia, triethanolamine and tetramethylethlenediamine.

[0046] A typical ink composition of the invention may comprise, forexample, the following substituents by weight: hyperbranched polymericdye (0.2-20%), water (20-95%), a humectant (5-70%), water miscibleco-solvents (2-20%), surfactant (0.1-10%), biocide (0.05-5%) and pHcontrol agents (0.1-10%).

[0047] Additional additives which may optionally be present in the inkjet ink composition of the invention include thickeners, conductivityenhancing agents, anti-kogation agents, drying agents, and defoamers.

[0048] The ink jet inks provided by this invention may be employed inink jet printing wherein liquid ink drops are applied in a controlledfashion to an ink receptive layer substrate, by ejecting ink dropletsfrom a plurality of nozzles or orifices of the print head of an ink jetprinter.

[0049] Ink-receptive substrates useful in ink jet printing are wellknown to those skilled in the art. Representative examples of suchsubstrates are disclosed in U.S. Pat. Nos. 5,605,750; 5,723,211; and5,789,070 and EP 813 978 A1, the disclosures of which are herebyincorporated by reference.

[0050] The following example illustrates the utility of the presentinvention.

EXAMPLES

[0051] The following dyes were used to prepare the hyperbranchedpolymeric dyes:

[0052] Synthesis of Hyperbranched Polymeric Magenta Dye HBPD-1

[0053] Tris(2-aminoethyl)amine (0.73 g), adipic acid (0.35 g), andmagenta Dye 1 (0.35 g) were dissolved in 11:11-methyl-2-pyrrolidinone/pyridine (70 wt. % relative to total amount ofstarting materials). Triphenyl phosphite (100 mol. % of amine) wasslowly added into the solution. The reaction mixture was heated at 80°C. for 3 hours under nitrogen. The solution was precipitated from coldether and purified by dialysis with water using a 1000 MW cut-off bagand followed by freeze drying.

[0054] Synthesis of Hyperbranched Polymeric Yellow Dye HPBD-2

[0055] Tris(2-aminoethyl)amine (0.87 g), adipic acid (0.15 g), andyellow Dye 2 (0.44 g) were dissolved in 11:11-methyl-2-pyrrolidinone/pyridine (70 wt. % relative to total amount ofstarting materials). Triphenyl phosphite (100 mol. % of amine) wasslowly added into the solution. The reaction mixture was heated at 80°C. for 3 hours under nitrogen. The solution was precipitated from coldether and dried at 40° C. under vacuum overnight.

[0056] Synthesis of Hyperbranched Polymeric Yellow Dye HPBD-3

[0057] Tris(2-aminoethyl)amine (0.59 g), adipic acid (0.15 g), andyellow Dye 2 (0.44 g) were dissolved in 11:11-methyl-2-pyrrolidinone/pyridine (70 wt. % relative to total amount ofstarting materials). Triphenyl phosphite (100 mol. % of amine) wasslowly added into the solution. The reaction mixture was heated at 80°C. for 3 hours under nitrogen. The solution was precipitated from coldether and dried at 40° C. under vacuum overnight

[0058] Synthesis of Hyperbranched Polymeric Yellow Dye HPBD-4

[0059] Tris(2-aminoethyl)amine (0.44 g), yellow Dye 2 (0.45 g) weredissolved in 11:1 1-methyl-2-pyrrolidinone/pyridine (70 wt. % relativeto total amount of starting materials). Triphenyl phosphite (100 mol. %of amine) was slowly added into the solution. The reaction mixture washeated at 80° C. for 3 hours under nitrogen. The solution wasprecipitated from cold ether and dried at 40° C. under vacuum overnight.

Comparative Example 1 (C-1) (Non-Polymeric Dye)

[0060] To prepare a comparative ink jet ink, 0.055 g of Dye 1, 0.05 gSurfynol® 465 (Air Products Inc.), 0.6 g glycerol, 0.1 gtriethanolamine, and 1.2 g diethylene glycol were added to 8.05 gdistilled water. The final ink contained 0.55% dye, 0.50% Surfynol® 465,6.0% glycerol and 2.0% diethylene glycol. The solution was filteredthrough a 3 μm polytetrafluoroethylene filter and filled into an emptyHewlett-Packard HP520 ink jet cartridge.

Comparative Example-2 (C-2) (Non-Polymeric Dye)

[0061] This ink was prepared similar to Comparative Ink 1 except thatDye 2 was used instead of Dye 1.

Example 1 of the Invention (I-1)

[0062] This ink was prepared similar to Comparative Ink 1 except thathyperbranched polymeric dye (HBPD-1) was used instead of Dye 1. Toprepare this ink, 0.5 g of HBPD-1, 0.05 g Surfynol® 465, 0.6 g glycerol,and 1.2 g diethylene glycol were added to 7.65 g distilled water. Thefinal ink contained 5% polymeric dye, 0.50% Surfynol® 465, 6.0% glyceroland 12.0% diethylene glycol. The solution was filtered through a 3 μmpolytetrafluoroethylene filter and filled into an empty Hewlett-PackardHP520 ink jet cartridge.

Example 2 of the Invention (I-2)

[0063] This ink was prepared similar to Example1 except thathyperbranched polymeric dye (HBPD-2) was used instead of hyperbranchedpolymeric dye (HBPD-1).

Example 3 of the Invention (I-3)

[0064] This ink was prepared similar to Example1 except thathyperbranched polymeric dye (HBPD-3) was used instead of hyperbranchedpolymeric dye (HBPD-1).

Example 4 of the Invention (I-4)

[0065] This ink was prepared similar to Example1 except thathyperbranched polymeric dye (HBPD-4) was used instead of hyperbranchedpolymeric dye (HBPD-1).

[0066] Printing

[0067] Elements were prepared using test images consisting of a seriesof 21 variable density patches, approximately 15 by 13 mm in size,ranging from 5% dot coverage to 100% dot coverage printed ontocommercially available Epson Premium Glossy Paper, Cat. No SO41286,Konica QP Photo IJ Paper (Catalog No. KJP-LT-GH-15-QP PI), KodakPhotographic Quality Paper, Cat. No 800 6298.a with a Hewlett-Packard HPDeskJet® 520 ink jet printer, using the above inks. The elements wereallowed to dry for 24 hours at ambient temperature and humidity.

[0068] Stability Tests

[0069] The above elements were then placed in an ozone chamber (˜100 ppbozone level, 50% relative humidity) for four weeks. Additional elementswere subjected to a smear test in a humidity chamber at 38° C., 80%relative humidity for one week. The Status A reflection densities of themaximum density patch of the elements were measured using an X-Rite® 414densitometer before and after the fade and smear tests. The percentagesof the Status A densities retained for the 100% dot coverage patcheswere calculated and are listed in Tables 1 and 2. For the smear test, apercentage of density retained higher than 100% indicates that there isa smear problem, and the deviation from 100% shows the degree of smear.TABLE 1 Element Containing Ozone Test Example Ink Receiver (% Retained)C-1 Epson Premium Glossy Paper 52 C-1 Konica QP 53 I-1 Epson PremiumGlossy Paper 88 I-1 Konica QP 73

[0070] TABLE II Element Containing Smear Test Example Ink Receiver (%Retained) C-2 Kodak Photographic Quality Paper 167 C-2 Konica QP 123 I-2Kodak Photographic Quality Paper 102 I-2 Konica QP 104 I-3 KodakPhotographic Quality Paper 96 I-3 Konica QP 100 I-4 Kodak PhotographicQuality Paper 97 I-4 Konica QP 105

[0071] The above results show that the elements of the invention hadimproved ozone stability and smear resistance as compared to the controlelements.

[0072] The invention has been described in detail with particularreference to certain preferred embodiments thereof, but it will beunderstood that variations and modifications can be effected within thespirit and scope of the invention.

What is claimed is:
 1. An ink jet ink composition comprising water, ahumectant, and a hyperbranched polymeric dye comprising a hyperbranchedpolymer having a dye chromophore pendant on the polymer chain orincorporated into the polymer backbone.
 2. The composition of claim 1wherein said hyperbranched polymer having a dye chromophore pendant onthe polymer chain has the formula: HB-D_(n) wherein: HB is ahyperbranched polymer core; D is a dye moiety; and n is an integer of atleast
 2. 3. The composition of claim 2 wherein said HB is a polyamide,polyester, polyether, vinylic polymer, polyimine, polysiloxane,polyesteramide or polyurethane.
 4. The composition of claim 2 whereinsaid HB is prepared by a chain polymerization of a monomer of theformula M¹-R¹M² _(m) wherein (i) R¹ is a linear or branched alkyl,carbonyl, or aromatic moiety; (ii), M¹ and M² are reactive groups thatreact independently of each other in which M¹ is a polymerization groupand M² is a precursor of a moiety M²* which initiates the polymerizationof M¹ as a result of being activated; and (iii), m is an integer of atleast
 1. 5. The composition of claim 2 wherein said HB is prepared by acondensation or addition polymerization of a monomer of the formulaM³-R²-M⁴ _(p) wherein (i) R² is a linear or branched alkyl or aromaticmoiety; (ii), M³ and M⁴ are groups that undergo a condensation oraddition reaction; and (iii), p is an integer of at least
 2. 6. Thecomposition of claim 2 wherein said HB is prepared by a condensation oraddition polymerization of a monomer of the formula R²-M⁵ _(q) and R³-M⁶_(t) wherein (i) R² is as defined above and R³ is a linear or branchedalkyl or aromatic moiety; (ii), M⁵ and M⁶ are groups that undergo acondensation or addition reaction; and (iii), q is an integer of atleast 2 and t an integer of at least
 3. 7. The composition of claim 4wherein M¹ is a non-substituted or substituted vinylic group, M² is X,—CH₂X or —CH(CH₃)X wherein X is Cl, Br, I, S—C(═S), YR⁴R⁵ or —O—NR⁴R⁵,Y═O or N, and R⁴ and R⁵ are each independently —(CH₂)_(r) (r=1-12),—C₆H₅, —C(O)O, or C(O).
 8. The composition of claim 5 wherein M³ and M⁴are each independently —COOH, —OH, —C(O)Cl, epoxy, anhydride, NH, orNH₂, and R² is —C₆H₃—, or —(CH₂)_(s)—C(R⁶)— wherein R⁶ is a linear orbranched alkyl or aromatic group and s is an integer of 1-14.
 9. Thecomposition of claim 6 wherein M⁵ and M⁶ are each independently —COOH,—OH, —C(O)Cl, epoxy, anhydride, NH or NH₂, and R³ is —C₆H₄—,—C₆H₄—O—C₆H₄—, —C₆H₃, N(CH₂)₃—, —C₄H₈—, —C₆H₁₀—,


10. The composition of claim 1 wherein said hyperbranched polymer havinga dye chromophore incorporated into the backbone thereof is a polyamide,polyester, polyether, vinylic polymer, polyimine, polyesteramide orpolyurethane.
 11. The composition of claim 1 wherein said hyperbranchedpolymer having a dye chromophore incorporated into the polymer backboneis prepared by a chain polymerization of a monomer of the formulaM¹-R⁷-M² _(m) wherein R⁷ is a linear or branched alkyl, carbonyl, oraromatic moiety containing a dye chromophore and M¹, M² and m aredefined as in claim
 4. 12. The composition of claim 1 wherein saidhyperbranched polymer having a dye chromophore incorporated into thepolymer backbone is prepared by a condensation or additionpolymerization of a monomer of the formula M³-R⁷-M⁴ _(p) wherein R⁷ isdefined in claim 11 and M³, M⁴ and p are defined as in claim
 5. 13. Thecomposition of claim 1 wherein said hyperbranched polymer having a dyechromophore incorporated into the polymer backbone is prepared by acondensation or addition polymerization of a monomer of the formulaR⁸-M⁵ _(q) and R⁹-M⁶ _(t) wherein R⁸ and R⁹ are each independently alinear or branched alkyl or aromatic moiety, at least one of whichcontains a dye chromophore, and M⁵, M⁶, q and t are defined as in claim6.
 14. The composition of claim 1 wherein said dye chromophore is amono- or poly-azo dye, basic dye, phthalocyanine dye, methine orpolymethine dye, merocyanine dye, azamethine dye, quinophthalone dye,thiazine dye, oxazine dye, anthraquinone or metal-complex dye.
 15. Thecomposition of claim 14 wherein said mono- or poly-azo dye is apyrazoleazoindole.
 16. The composition of claim 14 wherein saidmetal-complex dye is a transition metal complex of an8-heterocyclylazo-5-hydroxyquinoline.
 17. The composition of claim 1wherein said humectant is diethylene glycol, glycerol or diethyleneglycol monobutylether.
 18. The composition of claim 1 wherein saidhyperbranched polymeric dye comprises about 0.2 to about 20% by weightof said ink jet ink composition.